DE3611193A1 - N-SUBSTITUTED BENZAMIDES - Google Patents

Description

The invention relates to new N-substituted benzamides Process for their preparation and their use in Pesticides, in particular as insecticides and nematicides.

It is known that certain phosphoric acid ester amides such as e.g. B. O-ethyl-O- (3-methyl-4-methylthiophenyl) -N-isopropyl- phosphoric acid ester amide (free name: Fenamiphos) very have good insecticidal and nematicidal properties (see US Pat. No. 2,978,479 and the Pesticide Manual by British Crop Protection Council, 5th edition (1977), page 262 with a description of the commercial product Fenamiphos).

New N-substituted benzamides of the formula (I) found,

in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 represents} haloalkyl with more than one carbon atom or for cycloalkyl substituted by halogen or haloalkyl,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and represent hydrogen, halogen, nitro, alkyl, haloalkyl, haloalkoxy, haloalkylthio or the rest of -CONR ¹ R ² .

It was also found that the new N-substituted Benzamides of the formula (I) are obtained when benzoyl halides of the formula (II)

in which
R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are the} same or different and stand for hydrogen, halogen, nitro, alkyl, haloalkyl, haloalkoxy, haloalkylthio or for the rest -CO-Hal and
Hal stands for halogen,
with amines of the formula (III)

HNR ¹ R ² (III)

in which
R ¹ and R ^{2 have} the meanings given above,
or the corresponding hydrohalides, if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents.

Draw the new N-substituted benzamides of formula (I) distinguish itself through a very good nematicidal and insecticidal Effect out.

The invention preferably relates to compounds of the formula (I) in which
R ^{1 represents} hydrogen or alkyl having 1 to 6 carbon atoms,
R ^{2 represents} haloalkyl having 2 to 8 carbon atoms and 1 to 12 halogen atoms such as fluorine and / or chlorine, and also cycloalkyl having 3 to 8 carbon atoms substituted by halogen such as fluorine and / or chlorine and halogen-C ₁ -C ₂ -alkyl,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and are hydrogen, fluorine, chlorine, bromine, nitro, alkyl having 1 to 4 carbon atoms, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms in the alkyl part and 1 to 6 halogen atoms such as fluorine and / or chlorine and the radical -CONR ¹ R ² .

Particularly preferred are the new N-substituted benzamides of the formula (I) in which
R ^{1 represents} hydrogen or alkyl having 1 to 4 carbon atoms,
R ^{2 represents} haloalkyl having 2 to 6 carbon atoms and 1 to 8 fluorine or 1 to 8 fluorine and chlorine atoms and also cycloalkyl having 3 to 6 carbon atoms substituted by fluorine, chlorine and / or trifluoromethyl,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and are hydrogen, fluorine, chlorine, bromine, nitro, alkyl having 1 or 2 carbon atoms, haloalkyl, haloalkoxy or haloalkylthio each having 1 or 2 carbon atoms in the alkyl part and 1 to 4 fluorine and / or chlorine atoms as well as the rest of -CONR ¹ R ² .

The new compounds of the formula (I) in which
R ^{1 represents} hydrogen, methyl, ethyl, n-propyl, i-propyl or n-butyl,
R ² for 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 3-fluoroprop-1-yl, 3,3-difluoro-prop-1-yl, 3,3,3-trifluoro -prop-1-yl, 3-fluoroprop-2-yl, 3,3-difluoroprop-2-yl, 3,3,3-trifluoroprop-2-yl, 2-fluoro-2-methyl -prop-2-yl, 2,2-difluoro-2-methyl-prop-2-yl, 2-methyl-2,2,2-trifluoroprop-2-yl, 2-methyl-3,3,3 -trifluoroprop-1-yl, 2-methyl-3,3,3-chlorodifluoroprop-1-yl, 2-methyl-3,3,3-dichlorofluoroprop-1-yl, 1,3-difluoro - prop-2-yl, 1,1,1,3,3,3-hexafluoroprop-2-yl, 3-fluoro-2-fluoromethyl-prop-2-yl, 1,3-difluoro-2-fluoromethyl - prop-2-yl, 1-trifluoromethyl-cycloprop-1-yl and 2,2-difluorocycloprop-1-yl and
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and represent hydrogen, fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio and the rest of -CONR ¹ R ² .

Is used for example for the method according to the invention 2,6-difluorobenzoyl chloride and 2-amino-3,3,3-trifluoropropane as starting materials, the corresponding Reaction outlined by the following formula will:

Is used for example for the method according to the invention o-phthaloyl dichloride and 1-amino-3,3,3-trifluoropropane as starting materials, the corresponding reaction can be outlined by the following formula scheme:

Formula (II) provides a general definition of the benzoyl halides to be used as starting materials in the process according to the invention. In this formula, R ⁸ , R ⁹ R ¹⁰ , R ¹¹ and R ^{12 are} preferably hydrogen, fluorine, chlorine, bromine, nitro, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkoxy and halo-C ₁ -C ₄ alkylthio. Hal stands for halogen, in particular for fluorine or chlorine.

The compounds of formula (II) are known and / or can be produced by known methods. See, for example, DE-AS 21 23 236, DE-OS 26 01 780, DE-OS 26 37 947, DE-OS 32 17 619, DE-OS 32 17 620 and EP-OS 12 24 449.

Examples are the compounds of formula (II) called:

Hal = chlorine or fluorine

Table 1

Formula (III) provides a general definition of the amines to be used as starting materials in the process according to the invention and the corresponding hydrohalides. In this formula (III), R ¹ and R ² preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention. The hydrochlorides or the hydrobromides are preferably used as hydrohalides.

Examples are the compounds of formula (III) called:

HNR ¹ R ² (III)

Table 2

and the corresponding hydrochloride or bromide above compounds of formula (III).  

The compounds of formula (III) and the corresponding Hydrohalides are known in some cases (cf. e.g. J. Org. Chem. 24: 1256-1259 (1969); J. Org. Chem. 27. 1406-1409 (1962); Isvest. Akad. Nauk. SSSR, Ser. Khim. 1966, 226-228; Isvest. Akad. Nauk. SSSR, Ser. Khim. 1966, 1518-1523; J. Med. Chem. 22, 1130-1133 (1979); DE-OS 30 18 020; EP-A 39 813; DE-OS 32 18 966; EP-A 73 974; DE- OS 33 07 234; Ind. Eng. Chem. 48: 209-213 (1956); J. Am. Chem. Soc. 102, 4958-4959 (1980) and the preparation examples).

New amines falling under the formula (III) are, for example represented as follows.

New amines of the formula

in which the radicals X ¹ to X ^{3 can be} identical or different and stand for hydrogen or fluorine, at least one of the radicals X ¹ to X ³ standing for fluorine,
by manufacturing variant A)

• (a) the halogenated pivalic acid halides of the general formula (V) in which X ¹ to X ^{3 have} the meaning given above and Hal represents fluorine or chlorine,
  with a reagent which transfers azide groups into the fluorinated pivalic acid azides of the general formula (VI) in which X ¹ to X ^{3 have} the meaning given above, and
• (b) the optionally isolated compounds of the general formula (VI) thermally to the fluorinated isocyanates of the general formula (VII) in which X ¹ to X ^{3 have} the meaning given above, decomposes and
• (c) the optionally isolated compounds of general formula (VII) z. B. by hydrochloric acid hydrolysis in the fluorinated tertiary butylamine hydrochlorides of the general formula (VIII) in which X ¹ to X ^{3 have} the meaning given above, converts and
• (d) the optionally isolated compounds of the general Formula (VIII) by treatment with base in the fluorinated tertiary butylamines of the general Formula (IV) transferred.

or
by using process variant B)
the isocyanates of the formula (VII)

in which X ¹ to X ^{3 have} the meaning given above,
converted directly into the fluorinated tertiary butylamines of the general formula (IV) by alkaline hydrolysis,
or that in process variant C)
Pivalic acid amides of the general formula (IX)

in which X ¹ to X ^{3 have} the meaning given above,
reacted with hypohalite.

New cyclopropylamines of the formula (III) formula

are produced, for example, by the known Cyclopropylcarboxamines of the formula

reacted with sulfur tetrafluoride in anhydrous hydrogen fluoride in an autoclave.

Cyclopropanecarboxamines of the formula (XI) are known (see, e.g., J. Chem. Soc. 1960, 2119-2132, ibid. 1962, 3977-3980; Synthesis 1978, 46; Coll. Czech. Chem. Comm. 47, 2291-2305 (1982)).  

The inventive method for producing the new N-substituted benzamides of formula (I) is preferred performed using diluents. Water and practical come as a diluent all inert organic solvents in question. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, Hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, Benzene, toluene, xylene, methylene chloride, ethylene chloride, Chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, Ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, vinegar such as methyl acetate and ethyl esters, nitriles such as. B. acetonitrile and propionitrile, amides such as e.g. B. ditmethylformamide, dimethylacetamide and N-methyl-pyrrolidone and dimethyl sulfoxide, Tetramethylene sulfone and hexamethylphosphoric triamide.

As acid acceptors in process (I) according to the invention all usually for such implementations usable acid binders can be used. Preferably Alkali metal hydroxides such as z. B. sodium and potassium hydroxide, alkaline earth metal hydroxides such as e.g. B. Calcium hydroxide, alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, furthermore aliphatic, aromatic or heterocyclic Amines, for example triethylamine, trimethylamine, Dimethylaniline, dimethylbenzylamine, pyridine, quinoline, 1,5-diazabicyclo- [4,3,0] -non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] octane (DABCO). The amines of the formula (III) use in excess and the amine excess as Let the acid binder work.

The reaction temperatures can in the inventive Procedures can be varied over a wide range. in the generally one works at temperatures between 0 ° C and 100 ° C, preferably at temperatures between 20 ° C and 80 ° C- With reactive amines, heating is mostly hardly necessary because implementation is voluntary expires. If you have inert amines at Applying the implementation of the invention can take several hours Heating may be required.

The reactions are generally under normal pressure carried out. In the case of volatile and inert However, it can be advantageous to use amines in closed reactions Vessels and under increased pressure.

When carrying out the method according to the invention 1 -CO-Hal in the benzoyl halide of the formula (II) 1.00 to 1.6 moles, preferably 1.05 to 1.3 moles Amine of formula (III) and 1 to 3 moles, preferably 1 to 2 moles of acid acceptor or another mole of the amine Formula (III). Working up the reaction mixture takes place according to usual methods. The compounds of formula (I) usually come in a fixed formula or leave itself - if necessary after concentrating the reaction solutions - separate by adding water.  

With good plant tolerance and favorable toxicity to warm-blooded animals, the active substances are suitable for combating animal pests, in particular insects and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp ..
From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
From the order of the Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodaliphasum bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodop tera sppi, Trichoplapsia s., Trichoplusia n ., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Toronatrixia
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivususususususususususpp., Or , Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloitor. Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp ..
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, suspensions, Powders, foams, pastes, granules, aerosols, Active ingredient-impregnated natural and synthetic substances, Very fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals and. Ä., as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using surfactants Agents, ie emulsifiers and / or dispersants and / or foam-generating agents. In case of Use of water as an extender can e.g. Belly organic solvents used as auxiliary solvents will. Essentially come as liquid solvents in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, Alcohols, such as butanol or glycol, and their  Ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carrier substances are meant such liquids which at normal temperature and under normal pressure are gaseous, e.g. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are possible: e.g. B. natural rock flour, such as kaolins, clays, Talc, chalk, quartz, attapulgite, montmorrilonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granules come into question; e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; come as emulsifiers and / or foaming agents in question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene Fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants are: e.g. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well  natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be in their commercially available Formulations as well as in from these formulations prepared application forms in a mixture with others Active ingredients, such as insecticides, attractants, sterilants, Acaricides, nematicides, fungicides, growth regulators Substances or herbicides are present. Insecticides include, for example, phosphoric acid esters, carbamates, Carboxylic acid esters, chlorinated hydrocarbons, Phenylureas, substances produced by microorganisms u. a.

The active compounds according to the invention can also be used in their commercial formulations and in the from these Formulations prepared mixed use forms with synergists. Synergists are connections which increases the effectiveness of the active ingredients, without the added synergist itself being active have to be.  

The active substance content of those from the commercial formulations Prepared forms of application can be used in a wide range vary. The active substance concentration of the application forms can be from 0.0000001 up to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in one of the application forms adapted usual way.

When used against hygiene and storage pests the active ingredients are characterized by an excellent Residual effect on wood and clay as well as by a good Alkali stability on limed substrates.

As already explained above, the new compounds of the formula (I) according to the invention surprisingly have a particularly favorable toxicity to warm-blooded animals and, at the same time, a very good activity against animal pests in comparison with corresponding known compounds. In many cases, these properties can make the use of the active substances considerably easier, especially in cases where there is not enough experienced personnel available when applying the product and compliance with the usual precautionary measures and care required for pest control is not fully guaranteed.

Manufacturing examples example 1

17.65 g (0.1 mol) of 2,6-difluorobenzoyl chloride, dissolved in 50 ml of toluene, at 20 ° C-30 ° C to a solution of 11.30 g (0.1 mol) of 2-amino-1,1,1-trifluoropropane and 13.5 g (0.1 mol) of N, N-dimethylbenzylamine added dropwise in 200 ml of toluene and stirred at 50 ° C-60 ° C, where N, N-dimethylbenzylamine Hydrochloride fails. Then is at 20 ° C. cooled, extracted with water and the organic phase concentrated in vacuo. The colorless residue becomes White spirit and / or toluene recrystallized.

21.6 g (85.4% of theory) of 2,6-difluorobenzoic acid are obtained. N- (1,1,1-trifluoroprop-2-yl) amide of melting point 167 ° C-168 ° C.

Example 2

21.4 g (0.1 mol) of 2,3,4,5,6-pentafluorobenzoyl fluoride, dissolved in 50 ml of toluene, at 20 ° C-30 ° C to a  Solution of 9.9 g (0.1 mol) of 2,2,2-trifluoro-1-amino-ethane and 13.5 g (0.1 mol) of N, N-dimethylbenzylamine in 250 ml of toluene dripped. The mixture is then stirred at 50 ° C-60 ° C, cooled to 20 ° C, mixed with water and the suctioned off solid reaction product. The arrears with Washed water and dried.

25.2 g (86% of theory) of 2,3,4,5,6-pentafluorobenzoic acid are obtained. N- (2,2,2-trifluoroethyl) amide.

Example 3

18.55 g (0.01 mol) of 3-nitrobenzoyl chloride in 50 ml of toluene are at 20 ° C-30 ° C to a mixture of 14.95 g (0.1 mol) 2-amino-1,1,1-trifluoropropane hydrochloride and 27 g (0.2 mol) of N, N-dimethylbenzylamine added dropwise in 250 ml of toluene. The mixture is then stirred at 50 ° C-60 ° C. To Cooling to 20 ° C is mixed with water, and the solid Aspirated reaction product. The residue is washed with water washed and dried.

19.8 g (75.6% of theory) of 3-nitro-benzoic acid are obtained. N- (1,1,1-trifluoroprop-2-yl) amide of melting point 130 ° -131 ° C.  

Example 4

20.3 g (0.1 mol) of o-phthalchloride, dissolved in 100 ml Toluene, become a solution of at 20 ° C-30 ° C 22.6 g (0.2 mol) of 2-amino-1,1,1-trifluoropropane and 27.0 g (0.2 mol) of N, N-dimethylbenzylamine added dropwise in 300 ml of toluene. The mixture is then stirred at 50 ° C-60 ° C. To Cooling to 20 ° C is mixed with water and the solid Aspirated reaction product. The residue is washed with water washed and dried.

29.2 g (82% of theory) of o-phthalic acid bis- [N- (1,1,1-trifluoroprop-2-yl) amide melting at 230 ° C-231 ° C.

The following compounds can be used analogously to Examples 1 to 4 of formula (I):

Table 3

Starting compounds of the formulas (III) and (IIIa) Example (III-1)

H ₂ N-CH (CH ₂ F) ₂

45 g (0.2 mol) of N- (1,3-difluoro-2-propyl) phthalimide suspended in 100 ml of water and after adding 200 ml conc. Hydrochloric acid heated to reflux for 5 hours. The solid that precipitated after cooling (phthalic acid) is filtered off, the filtrate with 20% aqueous sodium hydroxide solution extracted and the extracts over magnesium sulfate dried. After distilling off the solvent at The residue becomes normal pressure in a water jet vacuum fractionated.

13.5 g (71% of theory) of 2- (1,3-difluoro) propylamine with a boiling point of 30-34 ° C./50 bar and a refractive index n = 1.3802 are obtained.

Example (IIIa-1)

40 g (0.4 mol) of 1-amino-cyclopropanecarboxylic acid are reacted with 100 g of SF ₄ and 50 ml of HF for 8 hours in a V ₄ A stirred autoclave at 120 ° C. under autogenous pressure (25-30 bar). After the volatile constituents have been distilled off, the mixture is made alkaline with 45% sodium hydroxide solution and the product is then separated off by steam distillation. The steam distillate is concentrated with. Hydrochloric acid made acidic.

After concentration and drying, 40 g (62% of the Theory) with 1-trifluoromethyl-cyclopropylamine hydrochloride a melting point ≦ λτ 260 ° C.

Example (IIIa-2)

To 32.4 g (0.2 mol) of 1-trifluoromethylcyclopropylamine hydrochloride from example (IIIa-1) 44 g (0.22 mol) 20% aqueous sodium hydroxide solution at 80 ° C-90 ° C oil bath temperature in about 15 min. dripped. At the same time it will released amine distilled off. After drying over magnesium sulfate is redistilled.

22 g (89% of theory) of 1-trifluoromethylcyclopropylamine with a refractive index n = 1.3483 are obtained.

The favorable toxicity of warm-blooded animals to the new compounds Formula (I) can be compared by the following values be demonstrated:

Example A

LD ₅₀ values in rats (oral)

The values were determined in the usual way. The active ingredients were made in polyethylene glycol LUTROL (trademark BASF Ag, Ludwigshafen, Federal Republic of Germany) dissolved and the solution administered to the rats by gavage.  

Example B

Limit concentration test

Test nematode: Globodera rostochiensis Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

The active ingredient preparation is mixed intimately with soil, which is heavily contaminated with the test nematodes. It plays the concentration of the active ingredient in the preparation is practical no matter, the decisive factor is the amount of active ingredient per volume of soil, which is given in ppm becomes. The treated soil is filled into pots and planted Potatoes and holds the pots at a greenhouse Temperature of 18 ° C.

After six weeks, the potato roots are on cysts examined and the effectiveness of the active ingredient determined in%. The efficiency is 100% when the infestation is complete is avoided, it is 0% if the infestation is accurate is as high as the control plants in untreated, but soil contaminated in the same way.

In this test, e.g. B. at drug concentrations of 2.5, 5 and 10 ppm, the compounds of the invention the manufacturing examples (1), (5), (29) and (33) and the known compound (A) has an efficiency of 95%.  

Example C

Limit concentration test / nematodes

Test nematode: Meloidogyne incognita Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water on the desired concentration.

The active ingredient preparation is mixed intimately with soil, which is heavily contaminated with the test nematodes. It plays the concentration of the active ingredient in the preparation is practical no matter, the decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm becomes. You fill the treated soil in pots, sow lettuce and keeps the pots at a greenhouse temperature of 27 ° C.

After four weeks, the lettuce roots become infected with nematodes (Root gall) examined and the efficiency of the Active ingredient determined in%. The efficiency is 100% if the infestation is completely avoided, it is 0% if the Infestation is just as high as in the control plants in untreated but contaminated soil in the same way.

In this test, at drug concentrations of 1.25 ppm- 10 ppm the compounds (1), (6) according to the invention, (29) and (33) and the known compound (A) one Efficiency of 95%.

Claims (10)

1. N-substituted benzamides of the general formula (I) in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 represents} haloalkyl with more than one carbon atom or for cycloalkyl substituted by halogen or haloalkyl,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and represent hydrogen, halogen, nitro, alkyl, haloalkyl, haloalkoxy, haloalkylthio or the rest of -CONR ¹ R ² . 2. N-substituted benzamides according to claim 1, characterized in that in the formula (I)
R ^{1 represents} hydrogen or alkyl having 1 to 6 carbon atoms,
R ^{2 represents} haloalkyl having 2 to 8 carbon atoms and 1 to 12 halogen atoms, such as fluorine and / or chlorine, and also halogen, such as fluorine and / or chlorine or halogeno-C ₁ -C ₂ -alkyl-substituted cycloalkyl having 3 to 8 carbon atoms,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and are hydrogen, fluorine, chlorine, bromine, nitro, alkyl having 1 to 4 carbon atoms, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms in the alkyl part and 1 to 6 halogen atoms and the radical -CONR ¹ R ² . 3. N-substituted benzamines according to claims 1 and 2, characterized in that in the general formula (I)
R ^{1 represents} hydrogen or alkyl having 1 to 4 carbon atoms,
R ^{2 represents} haloalkyl having 2 to 6 carbon atoms and 1 to 8 fluorine or 1 to 8 fluorine and chlorine atoms and also cycloalkyl having 3 to 6 carbon atoms substituted by fluorine, chlorine and / or trifluoromethyl,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and are hydrogen, fluorine, chlorine, bromine, nitro, alkyl having 1 or 2 carbon atoms, haloalkyl, haloalkoxy or haloalkylthio each having 1 or 2 carbon atoms in the alkyl part and 1 to 4 fluorine and / or chlorine atoms as well as the rest -CONR ¹ R ² . 4. N-substituted benzamides according to claims 1 to 3, characterized in that in the general formula (I)
R ^{1 represents} hydrogen, methyl, ethyl, n-propyl, i-propyl or n-butyl,
R ² for 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 3-fluoroprop-1-yl, 3,3-difluoroprop-1-yl, 3,3,3-trifluoro -prop-1-yl, 3-fluoroprop-2-yl, 3,3-difluoroprop-2-yl, 3,3,3-trifluoroprop-2-yl, 2-fluoro-2-methyl -prop-2-yl, 2,2-difluoro-2-methyl-prop-2-yl, 2-methyl-2,2,2-trifluoroprop-2-yl, 2-methyl-3,3,3 -trifluoroprop-1-yl, 2-methyl-3,3,3-chlorodifluoroprop-1-yl, 2-methyl-3,3,3-dichlorofluoroprop-1-yl, 1,3-difluoro -prop-2-yl, 1,1,1,3,3,3-hexafluoroprop-2-yl, 3-fluoro-2-fluoromethyl-prop-2-yl, 1,3-difluoro-2-fluoromethyl - prop-2-yl, 1-trifluoromethyl-cycloprop-1-yl and 2,2-difluorocycloprop-1-yl and
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and represent hydrogen, fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio and the rest of -CONR ¹ R ² . 5. Process for the preparation of N-substituted benzamides of the general formula (I) in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 stands} for haloalkyl with more than one carbon atom or for cycloalkyl substituted by halogen or haloalkyl.
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are the} same or different and represent hydrogen, halogen, nitro, alkyl, haloalkyl, haloalkoxy, haloalkylthio or the radical -CONR ¹ R ² ,
characterized in that benzoyl halides of the formula (II) in which
R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} identical or different and stand for hydrogen, halogen, nitro, alkyl, haloalkyl, haloalkoxy, haloalkylthio or for the rest -CO-Hal and
Hal stands for halogen,
with amines of the formula (III) HNR ¹ R ² , 6 (III) in which
R ¹ and R ^{2 have} the meanings given above,
or with the corresponding hydrohalides, if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents. 6. Pesticides, characterized by a content of at least one N-substituted Benzamide of formula (I). 7. Insecticides and nematicidal agents, characterized by containing at least one N-substituted Benzamide of formula (I). 8. methods of controlling insects and / or nematodes, characterized in that N-substituted Benzamides of the formula (I) on insects and / or Nematodes and / or their habitat can act. 9. Use of N-substituted benzamides of the formula (I) to control animal pests, in particular of insects and nematodes. 10. Process for the preparation of pesticides, characterized in that N-substituted Benzamides of the formula (I) with extenders and / or surfactants mixed.